TECHNICAL FIELD
[0001] The present invention relates to a casing for electronic equipment.
BACKGROUND ART
[0002] Polybutylene terephthalate resins have been used as engineering plastics in wide
uses including electronic equipment components, automobile components, and the like
because of excellent various properties such as mechanical properties, electrical
properties, and chemical properties, and satisfactory processability.
[0003] There is a need particularly for the casing among the electronic equipment components
to be provided with both impact resistance and flame retardance, and to be provided
with excellent low warpage so as to accommodate other components and to bond a case
with a lid.
[0004] There is disclosed, as a polybutylene terephthalate resin composition usable in the
electronic equipment components, a composition prepared by mixing a polybutylene terephthalate
resin with a modified polyester and a phosphinate (Patent Document 1). However, it
is difficult for this technology to satisfy both flame retardance and impact resistance
in the obtained molded article, and to obtain satisfactory low warpage required for
components such as a casing.
Patent Document 1: Japanese Unexamined Patent Application, Publication No. 2007-91865
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0005] An object of the present invention is to provide a casing for electronic equipment,
which is provided with both impact resistance and flame retardance, and is also provided
with excellent low warpage.
Means for Solving the Problems
[0006] The present inventors have found that the above problems can be solved by mixing
a polybutylene terephthalate resin (A) with a modified polyethylene terephthalate
resin (B), a halogen-free flame retardant (C), and an epoxy group-containing ethylene
copolymer (D), thus completing the present invention. More specifically, the present
invention provides the followings.
- (1) A casing for electronic equipment, composed of a polybutylene terephthalate resin
composition including:
a polybutylene terephthalate resin (A),
a modified polyethylene terephthalate resin (B),
a halogen-free flame retardant (C), and
an epoxy group-containing ethylene copolymer (D),
Wherein
the Charpy impact value measured in accordance with ISO-179 in the polybutylene terephthalate
resin composition is 10 kJ/m2 or more, and
the polybutylene terephthalate resin composition complies with 5VA standard at a thickness
of 2 mm in a test method in accordance with the UL 94 standard.
- (2) The casing for electronic equipment according to (1), wherein, when the total
amount of the polybutylene terephthalate resin (A) and the modified polyethylene terephthalate
resin (B) is 100% by mass, the polybutylene terephthalate resin (A) satisfies the
amount within a range of more than 50% by mass and less than or equal to 70% by mass,
and the modified polyethylene terephthalate resin (B) satisfies the amount within
a range of more than or equal to 30% by mass and less than 50% by mass.
- (3) The casing for electronic equipment according to (1) or (2), wherein the value
of the below-mentioned formula (I) represented by parts by mass of the modified polyethylene
terephthalate resin (B), the halogen-free flame retardant (C), and the epoxy group-containing
ethylene copolymer (D) based on 100 parts by mass of the polybutylene terephthalate
resin (A) is within a range of 2/8 or more and 3/7 or less.

- (4) The casing for electronic equipment according to any one of (1) to (3), wherein
the value of the below-mentioned formula (II) represented by parts by mass of the
modified polyethylene terephthalate resin (B) and the epoxy group-containing ethylene
copolymer (D) based on 100 parts by mass of the polybutylene terephthalate resin (A)
is within a range of 1/9 or more and 3/7 or less.

- (5) The casing for electronic equipment according to any one of (1) to (4), wherein
the value of the below-mentioned formula (III) represented by parts by mass of the
modified polyethylene terephthalate resin (B), the halogen-free flame retardant (C),
and the epoxy group-containing ethylene copolymer (D) based on 100 parts by mass of
the polybutylene terephthalate resin (A) is within a range of 0.8 or more and 1.0
or less.

- (6) The casing for electronic equipment according to any one of (1) to (5), which
is a casing accommodating components of any electronic equipment of the group consisting
of office automation equipment, electrical home appliances, or electric vehicles.
- (7) The casing for electronic equipment according to (6), wherein components of the
electronic equipment are power supply components.
Effects of the Invention
[0007] According to the present invention, there is provided a casing for electronic equipment,
which is provided with both impact resistance and flame retardance, and is also provided
with excellent low warpage.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Fig. 1 is a diagram showing a specimen made of a polybutylene terephthalate resin
composition of the present invention used to measure flatness.
PREFERRED MODE FOR CARRYING OUT THE INVENTION
[0009] An embodiment of the present invention will be described in detail below, but the
present invention is not limited to the following embodiment and variations can be
appropriately made without departing from the objects of the present invention.
Polybutylene Terephthalate Resin Composition
[0010] The casing for electronic equipment of the present invention is composed of a polybutylene
terephthalate resin composition containing a polybutylene terephthalate resin (A),
a modified polyethylene terephthalate resin (B), a halogen-free flame retardant (C),
and a thermoplastic polyester elastomer (D), and has prescribed properties. The respective
components and the like will be described below.
[Polybutylene Terephthalate Resin (A)]
[0011] The polybutylene terephthalate resin (A) used in the present invention is a polybutylene
terephthalate-based resin obtained by polycondensing a dicarboxylic acid component
containing at least terephthalic acid or an ester-forming derivative thereof (C
1-6 alkyl ester, acid halide, etc.) with a glycol component containing at least an alkylene
glycol having 4 carbon atoms (1,4-butanediol) or an ester-forming derivative thereof
(acetylated compound, etc.). The polybutylene terephthalate resin is not limited to
a homo-polybutylene terephthalate resin, and also may be a copolymer including 90
mol% or more of a butylene terephthalate unit.
[0012] In the polybutylene terephthalate resin (A) used in the present invention, examples
of the dicarboxylic acid component other than terephthalic acid and an ester-forming
derivative thereof (comonomer component) include a C
8-14 aromatic dicarboxylic acid such as isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic
acid, or 4,4'-dicarboxydiphenylether; a C
4-16 alkanedicarboxylic acid such as succinic acid, adipic acid, azelaic acid, or sebacic
acid; a C
5-10 cycloalkanedicarboxylic acid such as cyclohexanedicarboxylic acid; or an ester-forming
derivative of these dicarboxylic acid components (C
1-6 alkyl ester derivative, acid halide, etc.). These dicarboxylic acid components can
be used alone, or two or more of them can be used in combination.
[0013] Of these dicarboxylic acid components, a C
8-12 aromatic dicarboxylic acid such as isophthalic acid, and a C
6-12 alkanedicarboxylic acid such as adipic acid, azelaic acid, or sebacic acid are more
preferable.
[0014] In the polybutylene terephthalate resin used in the present invention, examples of
the glycol component other than 1,4-butanediol (comonomer component) include a C
2-10 alkylene glycol such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene
glycol, hexamethylene glycol, neopentyl glycol, or 1,3-octanediol; a polyoxyalkylene
glycol such as diethylene glycol, triethylene glycol, or dipropylene glycol; an alicyclic
diol such as cyclohexanedimethanol or hydrogenated bisphenol A; an aromatic diol such
as bisphenol A or 4,4'-dihydroxybiphenyl; a C
2-4 alkylene oxide adduct of bisphenol A, such as a 2 mol ethylene oxide adduct of bisphenol
A or a 3 mol propylene oxide adduct of bisphenol A; or an ester-forming derivative
of these glycols (acetylated compound, etc.). These glycol components can be used
alone, or two or more of them can be used in combination.
[0015] Of these glycol components, a C
2-6 alkylene glycol such as ethylene glycol or trimethylene glycol, a polyoxyalkylene
glycol such as diethylene glycol, or an alicyclic diol such as cyclohexanedimethanol
are more preferable.
[0016] Examples of the comonomer component used in the present invention other than the
dicarboxylic acid component and the glycol component include an aromatic hydroxycarboxylic
acid such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid,
or 4-carboxy-4'-hydroxybiphenyl; an aliphatic hydroxycarboxylic acid such as glycolic
acid or hydroxycaproic acid; a C
3-12 lactone such as propiolactone, butyrolactone, valerolactone, or caprolactone (ε-caprolactone,
etc.); or an ester-forming derivative of these comonomer components (C
1-6 alkyl ester derivative, acid halide, acetylated compound, etc.).
[0017] It is possible to suitably use, as the polybutylene terephthalate resin (A), all
polybutylene terephthalate copolymers obtained by copolymerizing the above-described
comonomer component. It is also possible to use, as the polybutylene terephthalate
resin (A), a homo-polybutylene terephthalate polymer in combination with a polybutylene
terephthalate copolymer so that the amount of the butylene terephthalate unit in the
obtained polybutylene terephthalate resin (A) is 90 mol% or more.
[0018] There is no particular limitation on the amount of a terminal carboxyl group of the
polybutylene terephthalate resin (A) used in the present invention, as long as the
objects of the present invention are not impaired. The amount of the terminal carboxyl
group of the polybutylene terephthalate resin used in the present invention is preferably
30 meq/kg or less, and more preferably 25 meq/kg or less. When using the polybutylene
terephthalate resin having a terminal carboxyl group in the amount within the above
range, the obtained polybutylene terephthalate resin composition is less likely to
undergo a decrease in strength due to hydrolysis in a moist heat environment.
[0019] The lower limit of the amount of the terminal carboxyl group of the polybutylene
terephthalate resin (A) is not particularly limited and is preferably 10 meq/kg or
more, and more preferably 5 meq/kg or more. Usually, it is difficult to produce a
polybutylene terephthalate resin having a terminal carboxyl group in the amount of
less than 5 meq/kg.
[0020] There is no particular limitation on an inherent viscosity of the polybutylene terephthalate
resin (A) used in the present invention, as long as the objects of the present invention
are not impaired. The inherent viscosity (IV) of the polybutylene terephthalate resin
(A) is preferably 0.60 dL/g or more and 1.2 dL/g or less so that the obtained polybutylene
terephthalate resin composition is particularly excellent in moldability. More preferably,
the inherent viscosity is 0.65 dL/g or more and 0.9 dL/g or less. It is also possible
to adjust the inherent viscosity by blending a polybutylene terephthalate resin having
a different inherent viscosity. For example, it is possible to prepare a polybutylene
terephthalate resin having an inherent viscosity of 0.9 dL/g by blending a polybutylene
terephthalate resin having an inherent viscosity of 1.0 dL/g with a polybutylene terephthalate
resin having an inherent viscosity of 0.7 dL/g. The inherent viscosity (IV) of the
polybutylene terephthalate resin (A) can be measured, for example, in an o-chlorophenol
under the conditions of a temperature of 35°C.
[Modified Polyethylene Terephthalate Resin (B)]
[0021] There have conventionally been used, as an opposite material for alloying, which
is excellent in compatibility with the polybutylene terephthalate resin (A), a polyethylene
terephthalate resin containing no modifying component, a modified polybutylene terephthalate
resin containing 10 mol% or more of a modifying component, and the like. However,
in the present invention, it is possible to obtain an electronic equipment casing,
which is particularly excellent in fluidity, warpage, and flame retardance, by using
a polybutylene terephthalate resin composition which contains a polyethylene terephthalate
resin (B) containing a prescribed modifying component.
[0022] The modified polyethylene terephthalate resin (B) used in the present invention is
a polyester resin obtained by polycondensing:
- 1) terephthalic acid or an ester-forming derivative thereof (C1-6 alkyl ester, acid halide, etc.),
- 2) ethylene glycol or an ester-forming derivative thereof (acetylated compound, etc.),
and
- 3) a modifying component which is dicarboxylic acid other than terephthalic acid,
an ester-forming derivative thereof (C1-6 alkyl ester, acid halide, etc.), glycol other than ethylene glycol, or an ester-forming
derivative thereof (acetylated compound, etc.)
in accordance with a known method.
[0023] Examples of dicarboxylic acid other than terephthalic acid, or an ester-forming derivative
thereof (C
1-6 alkyl ester, acid halide, etc.) include those exemplified for the component (A).
In the present invention, isophthalic acid is preferably used as the modifying component.
[0024] Examples of glycol other than ethylene glycol, or an ester-forming derivative thereof
(acetylated compound, etc.) include a C
2-10 alkylene glycol such as propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butylene
glycol, hexamethylene glycol, neopentyl glycol, or 1,3-octanediol; a polyoxyalkylene
glycol such as diethylene glycol, triethylene glycol, or dipropylene glycol; an alicyclic
diol such as cyclohexanedimethanol or hydrogenated bisphenol A; an aromatic diol such
as bisphenol A or 4,4'-dihydroxybiphenyl; a C
2-4 alkylene oxide adduct of bisphenol A, such as a 2 mol ethylene oxide adduct of bisphenol
A, or a 3 mol propylene oxide adduct of bisphenol A; or an ester-forming derivative
of these glycols (acetylated compound, etc.). These glycol components can be used
alone, or two or more of them can be used in combination.
[0025] The modifying component in the production of the modified polyethylene terephthalate
resin (B) used in the present invention may contain a hydroxycarboxylic acid component,
a lactone component, and the like, as long as the objects of the present invention
are not impaired. The amount of a repeating unit derived from these components in
the total repeating units in the polyethylene terephthalate resin (B) is preferably
5 mol% or more and 30 mol% or less, more preferably 7 mol% or more and 20 mol% or
less, and particularly preferably 10 mol% or more and 15 mol% or less.
[0026] Examples of the hydroxycarboxylic acid component contained in the modifying component
include an aromatic hydroxycarboxylic acid such as 4-hydroxybenzoic acid, 3-hydroxybenzoic
acid, 6-hydroxy-2-naphthoic acid, or 4-carboxy-4'-hydroxybiphenyl; an aliphatic hydroxycarboxylic
acid such as glycolic acid or hydroxycaproic acid; or an ester-forming derivative
of these hydroxycarboxylic acids (C
1-6 alkyl ester derivative, acid halide, acetylated compound, etc.). These hydroxycarboxylic
acid components can be used alone, or two or more of them can be used in combination.
[0027] Examples of the lactone component contained in the modifying component include a
C
3-12 lactone such as propiolactone, butyrolactone, valerolactone, or caprolactone (ε-caprolactone,
etc.). These lactone components can be used alone, or two or more of them can be used
in combination.
[0028] From the viewpoint of fluidity of the polybutylene terephthalate resin composition,
the modified polyethylene terephthalate resin (B) preferably has a melting point of
245°C or lower, and particularly preferably 240°C or lower. The melting point of the
modified polyethylene terephthalate resin (B) can be measured in accordance with JIS
K7121 using a differential scanning calorimeter (DSC).
[0029] Regarding the modified polyethylene terephthalate resin (B) in the polybutylene terephthalate
resin composition used in the present invention, in case the total amount of the polybutylene
terephthalate resin (A) and the modified polyethylene terephthalate resin (B) is 100%
by mass, it is preferable that the amount of the polybutylene terephthalate resin
(A) is more than 50% by mass and 70% by mass or less, and the amount of the modified
polyethylene terephthalate resin (B) is 30% by mass or more and less than 50% by mass.
It is more preferable that the amount of the polybutylene terephthalate resin (A)
is 55% by mass or more 65% by mass or less, and the amount of the modified polyethylene
terephthalate resin (B) is 35% by mass or more and 45% by mass or less. In case the
total amount of the polybutylene terephthalate resin (A) and the modified polyethylene
terephthalate resin (B) is 100% by mass, if the amount of the polybutylene terephthalate
resin (A) is 50% by mass or less, moldability of the polybutylene terephthalate resin
composition may deteriorate. In case the total amount of the polybutylene terephthalate
resin (A) and the modified polyethylene terephthalate resin (B) is 100% by mass, if
the amount of the polybutylene terephthalate resin (A) is more than 70% by mass, the
obtained molded article may exhibit undesirable appearance, warpage, and flame retardance.
[0030] The amount of the modified polyethylene terephthalate resin (B) for use in the polybutylene
terephthalate resin composition used in the present invention is preferably 30 parts
by mass or more and less than 100 parts by mass, and more preferably 40 parts by mass
or more and less than 100 parts by mass, based on 100 parts by mass of the polybutylene
terephthalate resin (A). When the amount of the modified polyethylene terephthalate
resin (B) is less than 30 parts by mass based on 100 parts by mass of the polybutylene
terephthalate resin (A), the obtained casing for electronic equipment may exhibit
undesirable appearance, warpage, and flame retardance. When the amount of the modified
polyethylene terephthalate resin (B) is 100 parts by mass or more based on 100 parts
by mass of the polybutylene terephthalate resin (A), moldability of the obtained polybutylene
terephthalate resin composition may deteriorate.
[Halogen-Free Flame Retardant (C)]
[0031] Examples of the halogen-free flame retardant (C) used in the present invention include,
but are not limited to, a phosphorous-based flame retardant, an antimony-based flame
retardant, and a nitrogen-based flame retardant.
[0032] The phosphorous-based flame retardant is not particularly limited, as long as it
is a compound having a phosphorus atom, and examples thereof include an organic phosphorous-based
flame retardant and an inorganic phosphorous-based flame retardant. Examples of the
organic phosphorous-based flame retardant include a phosphoric acid ester (aromatic
phosphoric acid ester such as triphenyl phosphate), a phosphoric acid ester amide,
a phosphonitrile compound ((poly)phenoxyphosphazene, etc.), an organic phosphonic
acid compound (phosphonic acid ester such as diphenyl methanephosphate or diethyl
phenylphosphonate), an organic phosphinic acid compound (methyl phosphinate, etc.),
and phosphine oxide (triphenyl phosphine oxide, tricresyl phosphine oxide, etc.).
[0033] Examples of the inorganic phosphorous-based flame retardant include a non-fused or
fused (phosphorous) phosphoric acid salt (metal salt such as a calcium salt), such
as red phosphorus, orthophosphoric acid, phosphorous acid, hypophosphoric acid, polyphosphoric
acid (metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric
acid, etc.), or polyphosphorous acid (metaphosphorous acid, pyrophosphorous acid,
etc.).
[0034] Examples of the antimony-based flame retardant include antimony trioxide, antimony
pentoxide, sodium antimonite, and the like. Examples of the nitrogen-based flame retardant
include a salt of a triazine-based compound with cyanuric acid or isocyanuric acid,
and a double salt of a nitrogen compound having an amino group with polyphosphoric
acid.
[0035] Of the above flame retardants, the organic phosphorous-based flame retardant is preferably
used in view of the fact that a toxic gas is not generated and high flame retardant
effect is exerted. The above flame retardants can be used alone, or two or more of
them can be used in combination.
[0036] The halogen-free flame retardant (C) in the polybutylene terephthalate resin composition
used in the present invention is preferably used so that the value of the below-mentioned
formula (I) represented by parts by mass of the modified polyethylene terephthalate
resin (B), the halogen-free flame retardant (C), and the epoxy group-containing ethylene
copolymer (D) described below based on 100 parts by mass of the polybutylene terephthalate
resin (A) is within a range of 2/8 or more and 3/7 or less.

[0037] When the amount of the halogen-free flame retardant (C) used is adjusted within the
above range, it is possible to satisfy both flame retardance and impact resistance
of the obtained casing for electronic equipment, preferably. When the value of the
formula (I), which represents the use amount of the halogen-free flame retardant (C),
is less than 2/8, it may be impossible to impart sufficient flame retardance to the
obtained casing for electronic equipment. When the value of the formula (I) exceeds
3/7, the obtained casing for electronic equipment may be insufficient in impact resistance.
[0038] The amount of the halogen-free flame retardant (C) for use in the present invention
used in the polybutylene terephthalate resin composition is preferably 40 parts by
mass or more and 100 parts by mass or less, and more preferably 50 parts by mass or
more and 65 parts by mass or less, based on 100 parts by mass of the polybutylene
terephthalate resin (A). When the above amount of the halogen-free flame retardant
(C) is contained in the casing for electronic equipment of the present invention,
the casing for electronic equipment can be preferably flame-retarded.
[0039] Since the casing for electronic equipment of the present invention is flame-retarded
by the halogen-free flame retardant, a toxic substance is less likely to be produced
and thus it is preferable from an environmental aspect.
[Epoxy Group-Containing Ethylene Copolymer (D)]
[0040] The epoxy group-containing ethylene copolymer (D) used in the present invention includes
an ethylene unit and an epoxy group-containing monomer unit as essential components,
and also includes an ethylenic unsaturated ester compound unit as an optional component,
and typical examples include a copolymer composed of 20 to 99.9% by mass of an ethylene
unit, 0.1 to 30% by mass of an epoxy group-containing monomer unit, and 0 to 50% by
mass of an ethylenic unsaturated ester compound unit. Examples of the epoxy group-containing
monomer include an unsaturated carboxylic acid glycidyl ester unit or an unsaturated
glycidyl ether unit.
[0041] Examples of the unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl
ether include a compound represented by the formula (IV):

wherein R represents an alkenyl group having 2 to 18 carbon atoms, and X represents
a carbonyloxy group, a methyleneoxy group, or a phenyleneoxy group. Specific examples
of such unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl
methacrylate, itaconic acid glycidyl ester, and the like. Examples of the unsaturated
glycidyl ether include allyl glycidyl ether, meta-allyl glycidyl ether, styrene-p-glycidyl
ether, and the like.
[0042] Examples of the ethylenic unsaturated ester compound include those other than the
glycidyl ester, for example, a vinyl ester of a saturated carboxylic acid, such as
vinyl acetate, vinyl propionate, or vinyl butyrate, or an alkyl ester of an unsaturated
carboxylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
ethyl methacrylate, or butyl methacrylate. Of these, vinyl acetate, methyl acrylate,
ethyl acrylate, methyl methacrylate, and the like are preferable. The amount of the
ethylenic unsaturated ester compound unit in the epoxy group-containing ethylene copolymer
(D) is usually within a range of 0 to 50% by weight, and is preferably within a range
of about 3 to 50% by weight when the ester compound unit exists.
[0043] The epoxy group-containing ethylene copolymer (D) in the present invention may be
any of a block copolymer, a graft copolymer, a random copolymer, and an alternating
copolymer and may be, for example, either a copolymer in which an epoxy group-containing
monomer is grafted onto a propylene-ethylene block copolymer, or a copolymer in which
an ethylenic unsaturated ester compound is grafted onto an ethylene-epoxy group-containing
monomer copolymer.
[0044] The epoxy group-containing ethylene copolymer (D) in the present invention can be
produced by copolymerizing a monomer to be provided for a known method, for example,
copolymerization in the presence of a radical generator under the conditions of about
500 to 4,000 atmospheric pressure and about 100 to 300°C, in the presence or absence
of an appropriate solvent and a chain transfer agent. It is also possible to produce
the epoxy group-containing ethylene copolymer (D) in the present invention by a method
in which polyethylene is mixed with an epoxy group-containing monomer and optionally
mixed with an ethylenic unsaturated ester compound, a radical generator, and the like,
and then the mixture is subjected to melt grafting copolymerization in an extruder.
[0045] The epoxy group-containing ethylene copolymer (D) can also be used in the form of
a mixture of the epoxy group-containing ethylene copolymer (D) and a rubber component.
Examples of such rubber component include an ethylene-based rubber, for example, a
rubber composed of an ethylene unit-α-olefin (having 3 or more carbon atoms) unit
such as an ethylene-propylene rubber, an ethylene-butene rubber, or an ethylene-butadiene
rubber, or a rubber composed of an ethylene unit-α-olefin (having 3 or more carbon
atoms) unit-nonconjugated diene unit such as an ethylene-propylene-nonconjugated diene
rubber; a styrene-based rubber such as a styrene-butadiene rubber, a SBS rubber, or
a hydrogenated SBS rubber; a polyisobutylene rubber, a butyl rubber, a butadiene rubber,
an isoprene rubber, an Alfie rubber, a nitrile rubber, a fluorine rubber, a vinyl
pyridine rubber, a silicone rubber, a butadiene-methyl methacrylate rubber, an acrylic
rubber, a urethane rubber, an epichlorohydrin rubber, a chlorobutyl rubber, a bromobutyl
rubber, and a mixture of two or more of these rubbers. It is also possible to use
these rubber components modified with a modifying agent such as maleic anhydride,
a halogenated compound, a vinyl compound, or an acrylic compound, as long as an adverse
influence is not exerted as a result of the excessive reaction with the epoxy group-containing
ethylene copolymer.
[0046] A mixture of an epoxy group-containing ethylene copolymer with a rubber component
can be obtained by a known method. The mixture can be produced, for example, by dry-blending
an epoxy group-containing ethylene copolymer with a rubber component, followed by
melt-kneading using a single or twin screw extruder, a Banbury mixer, a roll, various
kneaders, or the like.
[0047] The epoxy group-containing ethylene copolymer (D) in the polybutylene terephthalate
resin composition used in the present invention is preferably used so that the value
of the below-mentioned formula (II) represented by parts by mass of the modified polyethylene
terephthalate resin (B) and the epoxy group-containing ethylene copolymer (D) based
on 100 parts by mass of the polybutylene terephthalate resin (A) is within a range
of 1/9 or more and 3/7 or less.

[0048] When the amount of the epoxy group-containing ethylene copolymer (D) used is adjusted
within the above range, it is possible to satisfy both flame retardance and impact
resistance of the obtained casing for electronic equipment, preferably. When the value
of the formula (II), which represents the use amount of the epoxy group-containing
ethylene copolymer (D), is less than 1/9, it may be impossible to impart sufficient
impact resistance to the obtained casing for electronic equipment. When the value
of the formula (II) exceeds 3/7, the obtained casing for electronic equipment may
be insufficient in flame retardance.
[0049] The content of the epoxy group-containing ethylene copolymer (D) in the polybutylene
terephthalate resin composition used in the present invention is preferably 30 parts
by mass or more and 100 parts by mass or less, and more preferably 40 parts by mass
or more and 70 parts by mass or less, based on 100 parts by mass of the polybutylene
terephthalate resin (A), since impact resistance of the obtained molded article can
be satisfactorily improved to obtain a molded article having excellent mechanical
properties.
[0050] Furthermore, the polybutylene terephthalate resin (A), the modified polyethylene
terephthalate resin (B), the halogen-free flame retardant (C), and the epoxy group-containing
ethylene copolymer (D) in the polybutylene terephthalate resin composition are preferably
used so that the value of the below-mentioned formula (III) represented by parts by
mass of the respective components based on 100 parts by mass of the polybutylene terephthalate
resin (A) is preferably within a range of 0.8 or more and 1.0 or less.

[0051] When the amounts of the respective components used are adjusted within the above
range, it is possible to satisfy both flame retardance and impact resistance of the
obtained casing for electronic equipment, preferably. When the value of the formula
(III), which represents the use amounts of the respective components, is less than
0.8, it may be impossible to impart sufficient impact resistance to the obtained casing
for electronic equipment. When the value of the formula (III) exceeds 1.0, the obtained
casing for electronic equipment may be insufficient in flame retardance.
[Inorganic Filler]
[0052] It is preferable that the polybutylene terephthalate resin composition used in the
present invention contains, in addition to essential components, an inorganic filler.
Any of a fibrous filler, a particulate filler, and a platy filler may be used, and
two or more fillers may be used in combination as the inorganic filler.
[0053] A fibrous filler is preferably used in the present invention. This is because use
of the fibrous filler exerts the reinforcing effect to the molded article, thus enabling
an improvement in mechanical properties of the molded article. As the fibrous filler,
a glass fiber is particularly preferable. Known glass fibers are preferably used as
the glass fiber, and there is no particular limitation on diameter of the glass fiber,
shape such as cylindrical shape, cocoon-shaped cross section, or elliptic cross section,
or length or glass cutting method used in the production of a chopped strand, roving,
or the like. In the present invention, there is also no limitation on type of glass,
and E glass and a corrosion-resistant glass with the composition containing a zirconium
element are preferably used in view of quality. The fiber length and the fiber diameter
of the glass fiber may be within a usual range. For example, it is possible to use
a glass fiber having a fiber length of 2.0 mm or more and 6.0 mm or less, and a fiber
diameter of 9.0 µm or more and 14.0 µm or less.
[0054] The content of the fibrous filler in the polybutylene terephthalate resin composition
is not particularly limited, and is preferably within a range of 100 parts by mass
or more and 200 parts by mass or less, and more preferably 100 parts by mass or more
and 150 parts by mass or less, based on 100 parts by mass of the polybutylene terephthalate
resin.
[0055] In the present invention, a fibrous filler is preferably used in combination with
a platy filler. This combination use enables remarkable reduction in warpage while
imparting impact resistance to the molded article. Use of a glass fiber in combination
with a glass flake is particularly preferabe.
[0056] When using a fibrous filler in combination with a platy filler, the total amount
of the fibrous filler and the platy filler is preferably 100 parts by mass or more
and 200 parts by mass or less based on 100 parts by mass of the polybutylene terephthalate
resin. A ratio of the fibrous filler to the platy filler can be appropriately selected,
as long as the objects of the present invention are not impaired.
[Flame-Retardant Auxiliaries]
[0057] The polybutylene terephthalate resin composition used in the present invention preferably
contains, in addition to the above essential components, a flame-retardant auxiliary.
Satisfactory flame retardant effect can be obtained by using a flame retardant in
combination with a flame-retardant auxiliary. Type of the flame-retardant auxiliary
is not limited, as long as the objects of the present invention are not impaired,
and a suitable flame-retardant auxiliary can be selected and used according to type
of the halogen-free flame retardant (C).
[0058] When the organic phosphorous-based flame retardant is used as the halogen-free flame
retardant (C) used in the present invention, a nitrogen-containing flame-retardant
auxiliary is preferably used as the flame-retardant auxiliary. As the flame-retardant
auxiliary, melamine cyanurate is used particularly preferably.
[0059] The content of the flame-retardant auxiliary in the polybutylene terephthalate resin
composition is not particularly limited, and is preferably within a range of 20 parts
by mass or more and 40 parts by mass or less, and more preferably 25 parts by mass
or more and 35 parts by mass or less, based on 100 parts by mass of the polybutylene
terephthalate resin.
[Other Components]
[0060] The polybutylene terephthalate resin composition used in the present invention may
further contain other components, as long as the effects of the present invention
are not impaired. Examples of other components include additives such as a nucleating
agent, a pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant, a mold
releasant, and a dripping inhibitor, and other resins.
[0061] The content of other components in the polybutylene terephthalate resin composition
is not particularly limited, and is preferably 30 parts by mass or less, and more
preferably 20 parts by mass or less, in terms of the total amount, based on 100 parts
by mass of the polybutylene terephthalate resin (A).
[Method for Producing Polybutylene Terephthalate Resin Composition]
[0062] There is no particular limitation on a specific aspect of the method for preparing
a polybutylene terephthalate resin composition. A resin composition can be prepared,
for example, by a usually known facility and method as a method for preparing a resin
composition or a molded article thereof. Specifically, requisite components are mixed
and kneaded using a single or twin screw extruder or other melt kneader, thus making
it possible to prepare pellets for molding. A plurality of extruders or other melt
kneaders may be used. All components may be simultaneously introduced from a hopper,
and the components may be partially introduced from a side feed port.
Casing for Electronic Equipment
[0063] The casing for electronic equipment of the present invention is composed of the above-mentioned
polybutylene terephthalate resin composition. The phrase "the casing for electronic
equipment of the present invention is composed of the above-mentioned polybutylene
terephthalate resin composition" means that the casing for electronic equipment of
the present invention is obtained by molding the resin composition, and constituent
components of the casing for electronic equipment is partially or entirely derived
from the above-mentioned polybutylene terephthalate resin composition.
[0064] The casing for electronic equipment of the present invention can be produced, for
example, by molding the polybutylene terephthalate resin composition using a conventional
molding machine. Such molding machine is not particularly limited, as long as it can
be usually used for molding a casing for electronic equipment, and an injection molding
machine, a compression molding machine, and the like can be used. In view of excellent
ease of disposing metal components in a mold, simplicity of an apparatus, and productivity,
an injection molding machine is preferably used.
[0065] The electronic equipment, to which the casing for electronic equipment of the present
invention is applied, is not particularly limited, and is preferably any electronic
equipment of the group consisting of office automation equipment, electrical home
appliances, or electric vehicles. Since the casing for electronic equipment of the
present invention is provided with flame retardance and impact resistance, the casing
can be preferably used as a casing for accommodating components of such electronic
equipment. The casing for electronic equipment of the present invention is provided
with both impact resistance and flame retardance, and is also provided with excellent
low warpage. Therefore, it is also suited for bonding with components to be accommodated
inside, or bonding of a case with a lid, and can be preferably applied for electronic
equipment for which safety and satisfactory low warpage are required.
[Properties of Polybutylene Terephthalate Resin Composition and Casing for Electronic
Equipment]
[0066] The polybutylene terephthalate resin composition used in the present invention imparts
excellent impact resistance, flame retardance, and low warpage to a molded article.
[0067] Specifically, since the polybutylene terephthalate resin composition used in the
present invention exhibits the Charpy impact value as measured in accordance with
ISO-179 of 10 kJ/m
2 or more, the casing for electronic equipment of the present invention composed of
the polybutylene terephthalate resin composition is excellent in impact resistance.
Since the polybutylene terephthalate resin composition used in the present invention
complies with 5VA standard at a thickness of 2 mm in a test method in accordance with
the UL 94 standard, the casing for electronic equipment of the present invention composed
of the polybutylene terephthalate resin composition is excellent in flame retardance.
The casing for electronic equipment of the present invention is excellent in processability
such as bonding with components to be accommodated inside, or bonding of a case with
a lid since warpage is suppressed.
[0068] Since the casing for electronic equipment of the present invention has satisfactory
comparative tracking index, it is also provided with safety required for an electronic
equipment (particularly, power supply components).
EXAMPLES
[0069] The present invention will be described in more detail below by way of Examples,
but the present invention is not limited to the following Examples.
Materials
[0070] Details of the respective components used in Examples and Comparative Example are
as follows.
Polybutylene terephthalate (PBT): Polybutylene terephthalate with IV = 0.8, "DURANEX"
(registered trademark) manufactured by WinTech Polymer Ltd.
Modified polyethylene terephthalate (modified PET): 12.5 mol% Isophthalic acid-modified
polyethylene terephthalate, manufactured by Teijin Fibers Limited
Polyethylene terephthalate (unmodified PET): manufactured by Teijin Fibers Limited.
under the product name of TRF
Modified polybutylene terephthalate (modified PBT): 25 mol% Isophthalic acid modified
polybutylene terephthalate, manufactured by WinTech Polymer Ltd.
Flame retardant: Organic phosphate, manufactured by Clariant (Japan) K.K. under the
product name of Exolit OP1240
Flame-retardant auxiliary: Melamine cyanurate, manufactured by BASF Japan Ltd. under
the product name of MELAPUR MC50
Stabilizer: Sodium dihydrogen phosphate, manufactured by YONEYAMA CHEMICAL INDUSTRY
CO., LTD. under the product name of Sodium phosphate monobasic
Dripping inhibitor: PTFE, manufactured by Mitsubishi Rayon Co., Ltd. under the product
name of Metablen A3800
Glass fiber: E glass chopped strand, manufactured by Nippon Electric Glass Company,
Limited under the product name of ECS 03 T-187
Elastomer 1: Epoxy group-containing ethylene copolymer, manufactured by Sumitomo Chemical
Company, Limited under the product name of BONDFAST 7L
Elastomer 2: Polyester type polyester elastomer, manufactured by TOYOBO CO., LTD.
under the product name of Perplene S2001, hardness of 55
Elastomer 3: Polyether type polyester elastomer, manufactured by DU PONT-TORAY CO.,
LTD. under the product name of Hytrel 5557, hardness of 55
Elastomer 4: Core shell, manufactured by Rohm & Haas Japan K.K. under the product
name of Paraloid EXL2314
Elastomer 5: MBS resin, manufactured by Rohm & Haas Japan K.K. under the product name
of Paraloid EXL2602
Elastomer 6: Olefin, manufactured by Mitsui Chemicals, Inc. under the product name
of N TAFMER MP0620
"BONDFAST 7L" is a copolymer of ethylene, glycidyl methacrylate, and methyl acrylate.
"Perplene S" is a block copolymer including polybutylene terephthalate as a hard segment
and a soft polyester as a soft segment.
"Hytrel" is a block copolymer including polybutylene terephthalate as a hard segment
and polyether as a soft segment.
"Paraloid EXL2314" is a copolymer of an alkyl acrylate and an alkyl methacrylate.
"Paraloid EXL2602" is a copolymer of butadiene, an alkyl acrylate, and an alkyl methacrylate.
"N TAFMER MP0620" is a maleic anhydride-modified polyolefin.
"Hardness" means Durometer hardness (D scale) defined in JIS K7215.
Examples and Comparative Examples
[0071] Raw materials shown in Tables 1 and 2 were supplied in a twin screw extruder (TEX-30α,
manufactured by The Japan Steel Works, Ltd.), followed by melt-kneading to produce
a pellet-shaped polybutylene terephthalate resin composition. Melt-kneading conditions
are as follows. Units of numerals indicating the amount of each component in Tables
1 and 2 are parts by mass.
(Melt-Kneading Conditions)
[0072]
Cylinder temperature: 260°C
Screw speed: 170 rpm
Ejection amount: 20 kg/hour
(Molding Conditions of Specimens for Evaluation)
[0073] The obtained pellet-shaped resin composition was dried at 140°C for 3 hours, and
specimens were injection-molded under the following conditions.
Molding machine: ROBOSHOT S2000i100B, manufactured by FANUC Corporation
Cylinder temperature: 260°C
Mold temperature: 80°C (water temperature control)
Injection speed: 17 mm/second
Dwelling: 60 MPa × 20 seconds
[0074] With respect to the obtained specimens for evaluation, various properties were evaluated
under the following conditions. The results are shown in Tables 1 and 2.
(Tensile Test)
[0075] In accordance with evaluation criteria defined in ISO527-1,2, tensile strength and
tensile elongation of specimens for evaluation were evaluated.
(Flexural Test)
[0076] In accordance with ISO178, flexural strength and flexural elastic modulus of specimens
for evaluation were evaluated.
(Charpy Impact Value)
[0077] In accordance with evaluation criteria defined in ISO-179 (specimens of 4 mm in thickness),
the Charpy impact value of specimens for evaluation was evaluated.
(Melt Viscosity)
[0078] In accordance with ISO11443, the melt viscosity of the resin used in specimens for
evaluation was measured.
(Flame Retardance)
[0079] With respect to specimens for evaluation (0.8 mm in thickness, 2 mm in thickness),
UL 94 standard vertical flame test of UNDERWRITERS LABORATORIES INC. was carried out.
Judgment results for UL94 V-0, V-1, and V-2 standards with respect to each specimen
are shown in "UL94 flame retardance" in Tables 1 and 2. Judgment results illustrating
whether or not each specimen complies with 5VA of UL94 5VA and 5VB standard are shown
in "5VA flame retardance" in Tables 1 and 2.
(Warpage)
[0080] Flatness of plate-shaped specimens, each measuring 120 mm in length, 120 mm in width,
and 2 mm in thickness, was measured. Flatness of specimen was measured (9 points on
the specimen shown in Fig. 1) using a CNC image analyzer (product name; QVBHU404-PRO1F,
manufactured by Mitutoyo Corporation).
Evaluation criteria are as follows.
2 mm or less: A
2 to 5 mm: B
5 to 8 mm: C
8 mm or more: D
(Comparative Tracking Index (CTI))
[0081] In accordance with IEC112, 3rd Version, a comparative tracking index (CTI) of specimens
for evaluation was measured using an aqueous 0.1% ammonium chloride solution and platinum
electrodes. Based on the following evaluation criteria, the comparative tracking index
was rated.
250 to 400 V: 2
400 to 600 V: 1
More than 600 V: 0
[Table 1]
|
Example |
Comparative Example |
1 |
2 |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
PBT |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
Modified PET |
68.2 |
68.2 |
- |
67.9 |
68.2 |
68.2 |
68.2 |
68.3 |
68.3 |
Unmodified PET |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Modified PBT |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Phosphorus-based flame retardant |
55.7 |
61.8 |
32.5 |
49.2 |
49.9 |
75.5 |
54.9 |
70.9 |
78.4 |
Flame retardant auxiliary |
27.8 |
30.9 |
16.2 |
24.7 |
24.9 |
37.7 |
27.4 |
35.4 |
39.2 |
Stabilizer |
0.9 |
0.9 |
0.4 |
0.8 |
0.8 |
0.9 |
0.8 |
1.0 |
1.1 |
Dripping inhibitor |
0.9 |
0.9 |
0.4 |
0.8 |
0.8 |
0.9 |
0.8 |
1.0 |
1.1 |
Glass fiber |
128.5 |
132.5 |
64.9 |
105.5 |
124.7 |
141.5 |
117.6 |
151.9 |
224.0 |
Elastomer 1 |
42.6 |
42.5 |
- |
- |
42.6 |
42.6 |
18.6 |
73.2 |
42.8 |
Elastomer 2 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Elastomer 3 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Elastomer 4 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Elastomer 5 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Elastomer 6 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Tensile strength (MPa) |
85 |
83 |
91 |
90 |
87 |
73 |
97 |
75 |
98 |
Tensile elongation (%) |
2.8 |
2.7 |
1.3 |
2.2 |
2.9 |
2.4 |
2.2 |
3.3 |
2.3 |
Flexural strength (MPa) |
139 |
133 |
160 |
142 |
145 |
118 |
158 |
123 |
157 |
Flexural modulus (MPa) |
8610 |
8400 |
11200 |
9760 |
8990 |
8000 |
9300 |
7820 |
9330 |
Sharpy impact value (kJ /m2) |
10.4 |
10.2 |
5.5 |
6.0 |
10.6 |
7.2 |
8.1 |
12.0 |
7.8 |
Melt viscosity (kPa·s) |
0.50 |
0.52 |
0.35 |
0.33 |
0.48 |
0.63 |
0.38 |
0.70 |
0.65 |
UL94 flame retardancy |
0.8mm |
V-1 |
V-0 |
V-0 |
V-0 |
V-1 |
V-0 |
V-0 |
V-2 |
V-0 |
2mm |
V-0 |
V-0 |
V-0 |
V-0 |
V-2 |
V-0 |
V-0 |
V-2 |
V-0 |
5VA flame retardancy |
Compliable |
Compliable |
Compliable |
Compliable |
- |
Compliable |
Compliable |
- |
Compliable |
Warpage |
B |
B |
D |
B |
B |
B |
B |
B |
B |
CTI rank |
1 |
1 |
0 |
1 |
1 |
0 |
1 |
1 |
0 |
[Table 2]
|
Comparative Example |
8 |
9 |
10 |
11 |
12 |
13 |
14 |
15 |
16 |
17 |
PBT |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
Modified PET |
42.8 |
100.0 |
- |
- |
68.2 |
68.2 |
68.4 |
68.2 |
68.2 |
68.2 |
Unmodified PET |
- |
- |
68.2 |
- |
- |
- |
- |
- |
- |
- |
Modified PBT |
- |
- |
- |
68.2 |
- |
- |
- |
- |
- |
- |
Phosphorus-based flame retardant |
52.5 |
73.5 |
61.8 |
61.8 |
61.8 |
61.8 |
1 3.6 |
61.8 |
61.8 |
61.8 |
Flame retardant auxiliary |
26.3 |
36.8 |
30.9 |
30.9 |
30.9 |
30.9 |
57.0 |
30.9 |
30.9 |
30.9 |
Stabilizer |
0.8 |
1.1 |
0.9 |
0.9 |
0.9 |
0.9 |
1.4 |
0.9 |
0.9 |
0.9 |
Dripping inhibitor |
0.8 |
1.1 |
0.9 |
0.9 |
0.9 |
0.9 |
1.4 |
0.9 |
0.9 |
0.9 |
Glass fiber |
112.5 |
157.6 |
132.5 |
132.5 |
132.5 |
132.5 |
195.0 |
132.5 |
132.5 |
132.5 |
Elastomer 1 |
36.1 |
50.5 |
42.5 |
42.5 |
- |
- |
- |
- |
- |
- |
Elastomer 2 |
- |
- |
- |
- |
42.5 |
- |
- |
- |
- |
- |
Elastomer 3 |
- |
- |
- |
- |
- |
42.5 |
113.8 |
- |
- |
- |
Elastomer 4 |
- |
- |
- |
- |
- |
- |
- |
42.5 |
- |
- |
Elastomer 5 |
- |
- |
- |
- |
- |
- |
- |
- |
42.5 |
|
Elastomer 6 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
42.5 |
Tensile strength (MPa) |
82 |
Impossible to mold
(Mold release failure) |
84 |
85 |
97 |
90 |
69 |
69 |
78 |
41 |
Tensile elongation (%) |
2.5 |
2.7 |
2.8 |
1.8 |
2.2 |
2.5 |
2.5 |
1.8 |
0.7 |
Flexural strength (MPa) |
131 |
132 |
135 |
152 |
142 |
110 |
110 |
- |
- |
Flexural modulus (MPa) |
8430 |
8380 |
8320 |
10460 |
9760 |
6760 |
6760 |
- |
- |
Sharpy impact value (kJ/m2) |
10.1 |
10.1 |
10.1 |
6.6 |
7.2 |
7.8 |
6.4 |
6.6 |
3.1 |
Melt viscosity (kPa·s) |
0.58 |
0.67 |
0.51 |
- |
0.33 |
0.36 |
0.36 |
- |
- |
UL94 flame retardancy |
0.8mm |
V-2 |
V-0 |
V-2 |
V-0 |
V-0 |
V-1 |
V-1 |
V-1 |
V-1 |
2mm |
V-1 |
V-0 |
V-2 |
V-0 |
V-0 |
V-2 |
V-2 |
V-2 |
V-2 |
5VA flame retardancy |
- |
Compliable |
- |
Compliable |
Compliable |
- |
- |
- |
- |
Warpage |
C |
C |
B |
B |
B |
B |
B |
- |
- |
CTI rank |
1 |
1 |
1 |
1 |
1 |
1 |
1 |
2 |
1 |
[0082] The results of Examples revealed that a molded article provided with impact resistance,
tracking resistance, flame retardance, and suppressed warpage is obtained by mixing
a polybutylene terephthalate resin (A) with a modified polyethylene terephthalate
(B), a halogen-free flame retardant (C), and an epoxy group-containing ethylene copolymer
(D).